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Analytical Method for Flusulfamide as Benzenesulfonamide Fungicide, Residues in Major Agricultural Commodities

주요 농산물 중 Bezenesulfonamide계 살균제 Flusulfamide의 잔류 분석법

  • Ahn, Kyung-Geun (Department of Herbal Medicine Resource, Kangwon National University) ;
  • Kim, Gi-Ppeum (Department of Herbal Medicine Resource, Kangwon National University) ;
  • Hwang, Young-Sun (Department of Biology, University of Texas-Arlington) ;
  • Kang, In-Kyu (Department of Horticultural Science, Kyungpook National University) ;
  • Lee, Young Deuk (Division of Life and Environmental Science, Daegu University) ;
  • Choung, Myoung-Gun (Department of Herbal Medicine Resource, Kangwon National University)
  • 안경근 (강원대학교 생약자원개발학과) ;
  • 김기쁨 (강원대학교 생약자원개발학과) ;
  • 황영선 (텍사스주립대학교 생물학과) ;
  • 강인규 (경북대학교 원예과학과) ;
  • 이영득 (대구대학교 생명환경학부) ;
  • 정명근 (강원대학교 생약자원개발학과)
  • Received : 2018.01.31
  • Accepted : 2018.03.26
  • Published : 2018.03.31

Abstract

BACKGROUND: An analytical method was developed using HPLC-UVD/MS to precisely determine the residue of flusulfamide, a benzenesulfonamide fungicide used to inhibit spore germination. METHODS AND RESULTS: Flusulfamide residue was extracted with acetone from representative samples of five raw products which comprised apple, green pepper, Kimchi cabbage, hulled rice, and soybean. The extract was diluted with large volume of saline water and directly partitioned into dichloromethane to remove polar co-extractives in the aqueous phase. For the hulled rice and soybean samples, n-hexane/acetonitrile partition was additionally employed to remove non-polar lipids. The extract was finally purified by optimized Florisil column chromatography. On an octadecylsilyl column in HPLC, flusulfamide was successfully separated from co-extractives of sample, and sensitively quantitated by ultraviolet absorption at 280 nm with no interference. Accuracy and precision of the proposed method was validated by the recovery experiment on every crop sample fortified with flusulfamide at 3 concentration levels per crop in each triplication. CONCLUSION: Mean recoveries ranged from 82.3 to 98.2% in five representative agricultural commodities. The coefficients of variation were all less than 10%, irrespective of sample types and fortification levels. Limit of quantitation (LOQ) of flusulfamide was 0.02 mg/kg as verified by the recovery experiment. A confirmatory method using LC/MS with selected-ion monitoring technique was also provided to clearly identify the suspected residue.

본 연구에서는 HPLC-UVD/MS를 이용한 농산물 중 benzenesulfonamide계 살균제 flusulfamide의 잔류 분석법을 확립하였다. 대표 농산물은 사과, 고추, 배추, 현미 및 콩을 적용하였고, acetone에 의해 추출된 flusulfamide 성분을 dichloromethane 액-액 분배법과 Florisil 흡착크로마토그래피법으로 정제하여 HPLC-UVD/MS의 분석시료로 사용하였다. Flusulfamide의 정량적 분석을 위한 최적 HPLC-UVD 분석 조건을 검토하였으며, 정량한계(LOQ)는 0.02 mg/kg 이었다. 각 대표 농산물에 대해 정량한계, 정량 한계의 10배 및 50배 수준에서 회수율을 검토한 결과, 모든 처리농도에서 82.3-98.2% 수준의 회수율을 나타내었고, 반복간 변이계수(CV)는 최대 6.5%를 나타내어 잔류분석 기준인 회수율 70-120% 및 분석오차 10% 이내를 충족시키는 만족한 결과를 도출하였고, LC/MS/SIM을 이용하여 실제 농산물 시료에 적용하여 재확인 하였다. 이상의 결과로 신규 flusulfamide의 HPLC-UVD/MS 분석법은 검출한계, 회수율 및 분석오차 면에서 국제적 분석기준을 만족하는 신뢰성이 확보된 정량 분석법으로 사용 가능할 것이다.

Keywords

Acknowledgement

Supported by : Ministry of Food and Drug Safety, Kangwon National University

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